Fluorinated porous organic networks (F-PONs) have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported.Herein,using polydivinylbenzene (PDVB) as an easily available precursor,a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Brφnsted acid (trifluoromethanesulfonic acid).The afforded material (F-PDVB) featured high fluorine content(22 at.％),large surface area (771 m2·g-1),and good chemical/thermal stability,rendering them as promising candidates for the adsorption of CO2,hydrocarbons,fluorocarbons,and chlorofluorocarbons,with weight capacities up to 520 wt.％ being achieved.This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers (F-HCPs) from rigid aromatic monomers.The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.